Organophosphorus compounds derived from bis (halomethyl) oxetanes and thietanes



United States Patent 3,287,328 ORGANOPHOSPHORUS COMPOUNDS DERIVED FROM BIS(HALOMETHYL) OXETANES AND THI- ETANES Richard L. McConnell and Harry W. Coover, In, both of Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Original application Sept. 10, 1959, Ser. No. 839,053, now Patent No.. 3,041,350, dated June 26, 1962. Divided and this application Apr. 10, 1962, Ser. No. 190,996

Claims. (Cl. 260-79) This application is a division of our US. patent application Serial No. 839,053, filed September 10, 1959, now US. Patent 3,041,350.

This invention relates to new organophosphorus compounds and to a method for their preparation. In a specific aspect, this invent-ion relates to new organophosphorus esters and to methods ior their preparation. In another aspect this invention relates to new phosphorus-containing polymers and copolymers.

Many organophosphorus compounds have been (found useiul in recent years as insecticides, plasticizers, monomers for the preparation of polymers having unusual properties, as well as a variety of other uses. Acordingly, it is an object of this invent-ion to provide new organophosphorus compounds that have outstanding insecticidal activity and are useful in the preparation of polymeric materials. It is another object of this invention to provide a novel method for preparing these new organophosphorus compounds.

In accordance with this invention we have prepared new organophosphorus compounds having the structural fromula:

wherein R and X are as defined above and M is a radical selected iirorn the group consisting of hydrogen, -NH and alkali metals (sodium, potassium and lithium) with an oxetane or thietane having the structural formula:

C: CH

wherein X and Y are as defined above.

The reaction forming the compounds of this invention is usually carried out by slowly adding one of the reactants to the other reactant and any mode of addition of the reactants can be employed. The reaction is ordinairily carried out at a temperature within the range of 0 to 150 C. The molar ratio of reactants can be varied rather widely, but is is preferable to employ equal molar quantities of reactants for the most desirable results. The reaction is usually conducted in a solvent medium and among the solvents that are employed are lower aliphatic alcohols, ketones and normally liquid hydrocarbons. Suitable solvents aire normally liquid aliphatic and aromatic hydrocarbons such as pentane, hexane, hep-tane, octane,

3,287,328 Patented Nov. 22, 1966 benzene, toluene and xylene and alcohols such as ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, and the like. The period for reaction generally varies from about 1 to 8 hours.

The compounds of this invention and their preparation are described in the following examples:

Example 1.0,0-diethyl S-[(3-chl0romethyl-3- oxetanyl methyl] phosphorothiolothionate (C2Hn0)2P(S)SC{Iz/CH:C1

3,3-bis(chloromethyl) oxetane (0.1 mole) and the ammonium salt of diethyl phosphorothiolothionate (0.1 mole) were mixed in ml. or" absolute ethyl alcohol and heated to reflux with stirring for 4 hours. The precipitated ammonium chloride was filtered off and the solvent was removed under reduced pressure leaving the product as a transparent, straw-colored oil. N 1.5320, anal, calcd. for C H ClO PS P, 10.16. Found: P, 10.67. The infrared spectrum obtained on this compound was compatible with the proposed structure.

A similar product was obtained using the postassiurn and the sodium salt of diethyl phosphorothiolothionate rather than the ammonium salt.

Example 2.-0,0-diis0pr0pyl S-[(3-br0m0methyl-3- oxetanyl)methyl] phosphorothiolate This com-pound was prepared from 3,3-bis(bromomethyl) oxetane (0.1 mole) and the sodium salt of diethyl phosp horothiolate (0.1 mole) in refluxing isopropy-l alco hol according to the procedure of Example 1.

Example 3.Diethyl (3-chl0r0methyl-3-0xetanyl) methyl phosphate (C2H50)2P(O)OCH2 CHaCl This compound was prepared from the sodium salt of diethyl phosphate (0.2 mole) and 3,3-bis(chloromethyl) oxetane (0.2 mole) in refluxing ethyl alcohol according to the procedure of Example 1.

Example 4 .0,0-dimethyl S-[ (3-chlor0methyl-3- thietanyl) methyl]ph0sph0r0thi0late (CH O)iP(O)SC1'-I2 011 01 oE n CHg O 0,0-diethyl phosphorothiolothionate (0.1 mole), 3,3-

bis(iodomethyl)oxetane (0.1 mole), and pyridine (0.1

mole) were mixed in 200 ml. of benzene and refluxed on Example 6.Bulk polymerization of diethyl(3-chlor0- methyl-3-oxetanyl methyl phosphate Diethyl (3 chloromethyl-3-oxetanyl)methyl phosphate (10 g.) was treated with 0.2 ml. of boron trifluoride etherate. The temperature of the reaction mixture rose to a maximum of about 75. After standing for a short time, the polymer was opaque. The polymer was cured by heating at 150 in vacuo (0.1 mm.) to remove any volatile materials present. The solid polymer was triturated with ethyl ether and dried. The dried polymer is a white solid material with a softening point higher than 175 C. Flame-resistant fibers were drawn from the molten polymer and these were cold drawn to yield highly oriented specimens. The polymer was insoluble in the common solvents at 25 C. but it was soluble in hot chlorinated hydrocarbons, esters, and amines.

Similar polymers were obtained by polymerizing the products described in Examples 1, 2, 4, and 5 according to the process of Example 6.

Example 7.Solutin polymerization of 0,0-diethyl S- (3 chloromethyl-3-oxetanyl) methyl/phosphorothiolothionate Example 8.C0p0lymer of 0,0 dimethyl S-[(3-chloromethyl-.i-thietanyl)methyl]ph0sph0r0thi0late and 3,3- bis(chloromethyl) oxetane A mixture of 0,0-dimethyl S [(3 chloromethyl 3- thietanyl)methyl1phosphorothiolate (5 g.) and 3,3-bis (chloromethyDoxet-ane (5 g.) were polymerized in methylene chloride according to the procedure described in Example 7 to give a white solid polymer.

Example 9.C0p0lymer of 0,0-dz'ethyl S-[(3-iod0methyl-3-oxetanyl) methyl] phosphorothiolothionate and 3,3- bis(chloromethyl) oxetane A mixture of 0,0-diethyl S-[(3-iodomethyl-3-oxetanyl) methyl]phosphorothiolothionate (2.5 g.) and 3,3-bis (chloromethyl) oxetane (7.5 p g.) were polymerized in methyelne chlorine according to the procedure described in Example 7 to give a white solid polymer.

Example 10.C0p0lymer of diethyl (3-chloromethyl-3- oxetanyl)methyl phosphate and 3,3-bis(br0m0methyl) oxetane A mixture of diethyl (3-chloromethyl-3-oxetanyl)meth yl phosphate (7.5 g.) and 3,3-bis(bromomethyl)oxetane (2.5 g.) were polymerized according to the procedure of Example 6 to yield a white solid polymer.

Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, variations and modifications can be efl'ected within the spirit and scope of this invention as described hereinabove and as defined in the appended claims.

We claim:

1. As a composition of matter, a solid resinous polymer prepared by the polymerization of an organophosphorous compound having the structural formula:

C HzY wherein R is a lower alkyl radical containing from 1 to 4 carbon atoms, X is selected from the group consisting of oxygen and sulfur and Y is a halogen selected from the group consisting of chlorine, bromine and iodine in the presence of boron trifluoride etherate catalyst.

2. As a composition of matter, solid resinous polymers prepared by the homopolymerization of one compound designated by claim 1 in the presence of boron trifluoride etherate catalyst.

3. As a composition of matter, solid resinous polymers prepared by the copolymerization of any two compounds designated by claim 1 in the presence of boron trifluoride etherate catalyst.

4. As a composition of matter, solid resinous polymers prepared by the copolymerization of a compound designated by claim 1 with 3,3-bis(chloromethyl)oxetane in the presence of boron trifluoride etherate catalyst.

5. As a composition of matter, solid resinous polymers prepared by the copolymerization of a compound designated by claim 1 with 3,3-bis(bromomethyl)oxetane in the presence of boron trifluoride etherate catalyst.

References Cited by the Examiner UNITED STATES PATENTS 3,041,350 6/1962 McConnell et al 2602 3,071,594 1/1963 Enders et al. 260-327 3,209,013 9/1965 Hechenbleikner et a1.

LEON J. Bencovrrz, Primary Examiner.

WILLIAM H. SHORT, Examiner.

M. P. HENDRICKSON, M. I. MARQUIS,

Assistant Examiners. 

1. AS A COMPOSITTION OF MATTER, A SOLID RESINOUS POLYMER PREPARED BY THE POLYMERIZATION OF AN ORGANOPHOSPHOROUS COMPOUND HAVING THE STRUCTURAL FORMULA: 